Treatment of aliphatic and cyclic saturated hydrocarbons



Patented Aug. 13, 1935 PATENT OFFICE TREATMENT OF A-LIPHATIC AND CYCLIO SATURATED HYDROCARBONS Joseph J. Pelc, Chicago, Ill.

No Drawing. Application'August 17, 1934,

' Serial No. 740,350

28 Claims.

This invention relates to the direct treatment of aliphatic and cyclic saturated hydrocarbons, either pure or as they occur in mixture in crude petroleum and distillate fractions thereof, to pro duce directly therefrom saturated alcohols and other compounds as will more fully hereinafter appea Various attempts have been made heretofore to convert saturated hydrocarbons present in crude petroleum andin distillate fractions thereof into alcohols, aldehydes and other compounds. For example, treatment with nitric acid and also by chlorination has heretofore been proposed. I However, these attempts have not been entirely 511C) cessful and, so far as I am aware, there has not been proposed any method for the direct production-from saturated hydrocarbons of the character referred to of compounds such as alcohols, aldehydes, and other compounds .of the type referred to below. As 'a result of extensive research and experimentation I have developed a method of producing directly from aliphatic and cyclic saturated hydrocarbons numerous useful compounds, and it is to this method that the present invention relates.

The principal object of the present invention is the direct production of certain importantproducts from aliphatic and cyclic saturated hy-.

drocarbons, and particularly from crude petroleum or distillate fractions thereof.

An important object of the present invention is to provide for the direct production of saturated aliphatic alcohols from saturated aliphatic hydrocarbons.

for the direct production of cyclic saturated alcohols from cyclic saturated hydrocarbons, i. e. cycloparaflins.

A further object of the invention is to provide for the direct production of aliphatic aldehydes' from saturated aliphatic hydrocarbons. I A further object ofthe present invention is to provide for the direct production from saturated aliphatic hydrocarbon and from cycloparaflins of unsaturated, double-bonded hydrocarbons or substituted alkylenes formed by the addition of the aliphatic ketonic or aldehydic residue through the common aldehydic or ketonic group, i. e. the carbonyl group.

A further object of the invention is to provide for the direct production from. saturated aliphatic hydrocarbons of alkylenes having the same number of carbon atoms as the original saturated aliphatic hydrocarbons.

A further object of the present invention is to crude or purified state as motor or fuel oils, in

provide for the direct production of condensa- Another object of the invention is to provide provide for the direct production of compounds of the character referred to above not only from pure saturated hydrocarbons but especially from mixtures thereof as they occur in crude petroleum or any fraction or fractionsof crude petroleum. 5

A further object of the invention is to provide for the direct production of unsaturated; doublebonded compounds or drying oils, which are essentially alkylene's, or of oils containing mixtures of such unsaturated, double-bonded compounds 10 with aliphatic alcohols or aldehydes, such materials being directly produced from crude petroleum or any fraction or fractions of crude petroleum, the said oils being adapted for use in paints and lacquers, as solvents, perfumes, etc., or to be subjected to further treatment to produce pure fatty} acids therefrom.

A further object of the present invention is to 1:101! products bytheuse of aliphatic ketones. or 20 of polymerization products by the use of aliphatic aldehydes, from pure saturated hydrocarbons or mixtures thereof in crude petroleum or its fractions, such condensation and polymerization products being suitable for use in the production of resins and similar useful products.

A further object of the invention is to provide a method by which there can be produced direct- ]y from, and without any previous treatment of, saturated hydrocarbons, such compounds as alcohols, aldehydes and other compounds which can be readily purified, isolated and treated further to produce such products as fatty acids, for example. v

A further object of the invention is to provide a method by which compounds analogous to those just referred to can also be produced directly, asfar as they are structurally possible,

. from cycloparaffins.

Other objects and advantages of the present invention will become apparent during the course ofthe following description,

In its broad aspect the presentdnvention consists of reacting a saturated aliphatic hydrocarbon or a cyclic saturated hydrocarbon with an aliphatic aldehyde or ketone in the presence of I an activating agent. According tothe manner in which the reaction is regulated and controlled,

various products may be produced as willmore 5o having the type formula CnH2n+2, such as methane, ethane and the like. The invention is also adapted for the treatment of cyclic saturated hydrocarbons, i. e. cycloparaflins, having the type formula CnHZn, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like. As is indicated above, pure hydrocarbons of the above referred to character may be treated according to the present invention but the invention is particularly concerned with the treatment of mixtures of such hydrocarbons as they appear in crude petroleum and distillate fractions thereof, such as kerosene, gasoline, petroleum ether and the like.

As indicated above, the saturated hydrocarbon or mixture of hydrocarbons is reacted with an aliphatic aldehyde or ketone. While any aliphatic aldehyde may be employed in the practice of the process I prefer to employ paraand meta aldehydes, such as paraformaldehyde,

metaformaldehyde, paraldehyde and the like,

and prefrably paraldehyde. Similarly, various ketones may be used such as acetone, diethylketone, ethylmethylketone, and such compounds as substituted ketones in the nature of hydroxyacetone, but I prefer to employ acetone because of its complete-suitability and relatively low cost.

As pointed out above, the reaction between the saturated hydrocarbon under treatment and the aliphatic aldehyde or ketone is effected in the presence of an activating agent. The activating agent may consist of an elevated temperature, preferably of the order of 500-800 C. In other words, the reaction may-be effected by heating the hydrocarbon with the reacting'agent to a relatively high temperature. In this case the heat to which the materials are subjected serves as an activating agent to promote the reaction.

Instead of the use of heat as an activating agent, I may use certain chemical compounds as activating agents, in which case it is not necessary to effect the reaction at an elevated temperature. The chemical compound serving as an activating agent for the reaction may be a catalyst such as inorganic oxides and hydroxides, halogen acids, or sulfur oxides and sulfuric'acid or mixtures thereof. I may also employ an activating agent consisting of inorganic halides other than alkali metal halides. Such halides serve in effect as catalysts although they do not act strictly as catalysts since they react to form halides with the organic compounds present. However, these halides formed are very readily broken down and the halides may be recovered in their original form. Thus, in the case of all of the chemical.

activating agents employed, the chemical compounds used may be substantially completely recovered and reused in the further practice of the process.

Referring to the chemical activating agents which may be used in the practice of the process,

as an inorganic oxide I may employ soda lime,

calcium oxide or the like. Caustic soda is the hydroxide preferably employed although other inorganic hydroxides such as potassium hydroxide, calcium hydroxide or the like may be used. Any inorganic halide except alkali-metal halides may be used as an activating agent. Calcium chloride and beryllium chloride are 'examples. Any of the halogen acids such as hydrochloric acid, hydrobromic acid or the like may be used. When any of the foregoing chemical activating agents are employed they must be used in great excess, generally to the extent of four times or more the volume-of the mass of organic reacting agents present.

Where the reaction between the saturated nydrocarbon and the aliphatic aldehyde or ketone is effected in the presence of an activating agent comprising heat or one of the chemical activating agents just referred to, the yields are so small that the process may scarcely be said to be of commercial importance. However, for the sake of completeness several examples of the process using such activating agents will be set forth. 1

The process assumes real commercial importance when the activating agent employed is a sulfur oxide or sulfuric acid, or mixtures thereof. For example, sulfur dioxide or sulfur trioxide may be introduced in gaseous form into the reacting mass. However, in commercial practice I prefer to employ a relatively strong sulfuric acid as the activating agent. As will hereinafter appear, sulfuric acid of various strengths may be employed.

In commercial practice I prefer to react crude petroleum or a distillate fraction thereof with acetone or paraldehyde in the presence of sulfuric acid. By thecontrol of the operating conditions, such as time, temperature, proportions of ingredients, etc., several different compounds can be produced as a result of the reaction. Examples of several such modifications will be hereinafter set forth in detail.

While it is more of scientific interest than of commercial importance, saturated alcohols may be produced by mixing an aliphatic saturated hydrocarbon or a cycloparaflin with an aliphatic ketone or aldehyde and heating the mixture at an elevated temperature, say from 500 to 800 C. Instead of treating the hydrocarbons themselves, mixtures of the same may be treated. For example, equal parts of gasoline and acetone or acetaldehyde are mixed in solution or in the form of an intimate suspension and the solution or mixture passed once or repeatedly through a tube or pipe, or heated in sealed tubes, at say from 500 to 800 C. As a result of this treatment certain amounts of aliphatic alcohols are produced, the treated mass containing not only the aliphatic alcohols but also a portion of the substances originally used in undecomposed condition, polymerization or condensation products, and also unsaturated, double-bonded compounds derived from the saturated hydrocarbons treated.

It may be here pointed out that the reactions which take place as well as all of the reactions described-below are based essentially upon the reactivity of the carbonyl group which is common to both aldehydes and ketones. For this reason the reactions of both the aliphatic aldehydes and ketones are hereinafter jointly treated.

While there is a certain yield of desirable products such as aliphatic alcohols when the above referred to reaction is effected at an elevated temperature, better yields are obtained when the reaction is efiected in the presence of an activating agent such as inorganic oxides, hydroxides or halides, such as chlorides, excepting alkali-metal halides. Where halides are employed'they should be absolutely dry. Yields are increased if the saturated hydrocarbons or their mixtures are dissolved in the respective aliphatic aldehydes or ketones and the mass is supersaturated or impregnated with an inorganic oxide, hydroxide, or dry halide by vigorous mixing.

-naphthenic acids.

ally also oxidized in 'this case to a mixture of In some cases, especially when aliphatic aidehydes are employed, polymerization products predominate in the reaction mam after, neutralization, as hereinafter referred to, but nevertheless alcohols and unsaturated, double-bonded compounds can be isolated either directly or by depolymerization of the product of polymerization between the aliphatic aldehyde and saturated hydrocarbon.

As an example of the use of a hydroxide as I,

the'kerosene as by mechanical stirring. To themixture is then added not less than two or three parts by weight of dried sodium hydroxide, say in flakes. The amount of caustic soda employed may vary somewhat but it should be used in suii'icient amount to make the mixture nearly solid. The resulting mixture is introduced into a vessel which is covered tightly to exclude air and moisture therefrom. The mixture is kept out of contact with the air for not less than one week with occasional addition of more caustic soda if the mixture starts to liquefy. At the end of about one week the mixture may be removed from the vessel and dissolved in water, in which case the mass will contain the products of the kerosene hydrocarbons such as unsaturated double-bonded hydrocarbons, alcohols, such for example, as decyl alcohol and double-bonded additive compounds of cycloparaiiins andthe ketone such, for example, as 1,1 dimethylcyclopentylethylene. If, instead of keeping the mixture for only about one week before dissolving it in water it is kept longer, say about two weeks,

the reaction mass usually dissolves completely in water and on neutralization with acid, such as an inorganic acid, yields organic acids of the respective hydrocarbons of kerosene including The ketone present is usuacids.

The same process as just described may re-, peated with crude petroleum or any fraction of.

crude petroleum. Where gaseous hydrocarbons are employed they generally require larger quantities of the aliphatic aldehydes or ketones, since they must be kept in solution. Some aliphatic aldehydes give only very small quantities of alco hols and unsaturated compounds from the saturated hydrocarbons used.

The foregoing process is somewhat faster when the reaction is conducted in the presence of inorganic oxides, for example, alkali metal oxides.

It is also faster 'when certain chlorides, such as beryllium chloride, arev employed as activating agents although with some chlorides the reaction is very slow. However, in principle the reactivity of the carbonyl group causes in all of these cases the formation of certain amounts of alcohols and ketone, the yields of the alcohols and other compounds from the saturated hydrocarbons used are much higher. Generally, there are formed the respective halides of the saturated hydrocarbons used and of their compounds with aldehydes and ketones. However, these halides may be readily broken down.

In principle, the process is the samein all of the.

modifications described above since the reaction between the saturated hydrocarbons and the aldehydes or ketones goes first through the carbonyl group. However: as indicated above, the yields resulting from the practice of the several modifications of the process described above are relatively small with the result that these modiflca-.

tions are not suitable for best commercial practice but are more of scientific than commercial: interest. 'For satisfactory commercial practice it is necessary that the process be so conducted as to insure maximum quantitative yields bythe use of inexpensive reagents that react directly upon the hydrocarbons and to provide for the recovery of all of these reagents or at least one of them. I have accomplished this desired result by providing a modification ofthe general process described above by which aldehydes, alcohols, unsaturated compounds, and condensation and polymerization products can readily be produced directly from the hydrocarbons or mixtures thereof and isolated and purified. In this modification, I employ a sulfur oxide orsulfuric acid as the activating agent for the reaction referred to. In commercial practice it is most advantageous to employ sul furic acid and this material will be used for the purpose of specific illustration in the further description of this modification of the process. While it is ordinarily advisable to use concentrated sulfuric acid as the activating -agent, the acid does not have to be concentrated since, for example, even a 75 per cent. acid can activate the reaction. However, the reaction is much slower and, therefore, a- ,concentrated acid is recommended.

As indicated above, I may react with the saturated hydrocarbon to be treated either an aliphatic aldehyde or ketone, sulfuric acid being'employed as an activating agent to promote the reaction. Th reactions which occur when aldehydes and ketones are employed will be separately considered. 1

When aliphatic aldehydes act upon a saturated hydrocarbon under the activation of sulfuric acid,

1 polymerization .products are mostly formed.

However, even under these circumstances it is possible to isolate from the reaction mass certain alcohols and unsaturated compounds formed by the reaction of the saturated hydrocarbons with the aliphatic aldehydes used, not only by the direct method but also by the depolymerization of the products of polymerization.

When it is desired to react upon saturated hydrocarbons either as such or in mixture, such as in crude petroleum or fractions thereof, with an aliphatic aldehyde, strong sulfuric acid being-used as an activating agent, it is preferable to' employ metaldehydes and paraldehydes. Lower aldehydes can be used in vaporized state when convenient but for obvious reasons, it is much better to use themetaldehydes and paraldehydes directly inconnection with strong sulfuric. acid.

As a specific example of the modification of in the reaction, I maytake one, molecular equivalent of comparatively pure hexane and, while cooling the mass,.mix it with slightly more than one molecular equivalent of concentrated sull the process wherein an aliphatic aldehyde is used I furic acid (66 B.). There is gradually added to this mixture with careful outside cooling to keep the temperature of the mass at about'5 C. slightly more than one molecular equivalent of paraldehyde calculated as acetaldehyde. In approximately one-half hour the mixture nearly solidifies and the mass is then treated with say "soda ash in an amount suflicient to neutralize the sulfuric acid present. As a result of this treatment there is obtained a reddish solid polymerization product formed of hexane and paraldehyde used. This product can be recrystallized, purified and obtained in nearly white state. It is generally quite stable but on heating it ordinarily dissointermediate product was identified as 1 methyl,

2 pentylethylene This reaction was repeated also with paraformaldehyde and other accessible aldehydes. It

. was also applied to gasoline, the polymerization product of which behaves in a similar way as that of pure hexane. Other hydrocarbons and their mixture, including crude petroleum give the same reaction. In the case of higher aldehydes one or both chains sometimes may be broken but, in principle, the reaction of the carbonyl group is the same. This-is also true in connection with the higher ketones.

While aliphatic aldehydes may be employed in the practice of the present invention as indicated above, it is preferable to use ketones instead of the aldehydes. From a commercial standpoint, the lowest ketones, and particularly acetone, are best suited for the process. Acetone is hereinafter specified for the purpose of illustration since acetone illustrates to best advantage all of the steps and mechanics of the reaction referred to above and also since all intermediate products leading up to the condensation products can be isolated and the yields are substantially quantitative and the products comparatively pure. While acetone is hereinafter specified for the sake of convenience, it is, of course, to be understood that this compound is used solely for the purpose of specific illustration. Other ketones and also aldehydes react in a generally similar way. Of course, where aldehydes are employed polymerization products are obtained whereas when ketones are employed condensation products are obtained. Also, there is naturally a specific difference between the intermediate products obtained when aldehydes and ketones are used. For example, where acetaldehyde is used, the substituted or additive alkylenes produced are 1.

methyl, 2 alkyl ethylenes whereas when acetone is employed the substituted or additive alkylenes are 1,1 dimethyl, 2 alkyl ethylenes or 2 methyl, 2 alkyl ethylenes.

Where acetone is reacted with a saturated allphatic hydrocarbon or a cycloparaflin in the presence of sulfuric acid under uncontrolled conditions there are formed almost exclusively condensation products of acetone with itself. However, while acetone and all other aliphatic ke-' tones and aldehydes doform a great number of compounds between themselves and the saturated hydrocarbons treated, I have discovered that by controlling and regulating the reaction the production of certain specific products may be obtained. For example, by modifying the concentrations of the hydrocarbon, acetone and sulfuric acid and also by varying the time of treatment and the temperature of operation the production of certain specific compounds may be efiected. The regulation and control of the reaction to produce particular compounds will be apparent from the several examples of this modification of the process set forth below.

While in a broad sense thepresent invention depends upon the reactivity of the carbonyl group in the reaction between an aliphatic aldehyde or a ketone with saturated aliphatic hydrocarbons and cycloparafiins, it also depends specifically upon the formation of substituted or additive alkylenes and their subsequent regulated decomposition in different acid and alkali concentrations.'

From a scientific standpoint, my process is based upon the formation of carbinols and alkylenes and the subsequent direct decomposition and transformation of the alkylenes to form alcohols and aldehydes and also polymerization and condensation products. In order that the general scheme or mechanics of the present process may be readily apparent, there is set forth below a series of reactions which may take place when a saturated hydrocarbon is reacted with a ketone in the presence of sulfuric acid. The process may be so conducted that it may be terminated at the end of the first reaction or, as where the production'of aldehydes is the goal, all of the reactions will take place successively before the production of the final product. The extentto which the reactions are caused to take place will depend upon the manner in which the treatment is regulated. Generally speaking, the time of treatment and the concentration of hydrocarbon present may be considered as fixed constants and the extent to which the successive reactions occur is primarily dependent upon the increase in the concentration of the ketone and sulfuric acid.

For example, assuming that hexane is reacted with a certain concentration of acetone in the presence of a certain concentration of sulfuric acid, and the reaction product treated with an alkali, such as sodium carbonate, as is hereinafter described in detail, there may be produced as the final product from the hexane and acetone employed an additive carbinol, which may be indicated in a general way as follows:

The foregoing equation is, as stated, merely a general indication of the formation of an additive carbinol from the hexane and acetone employed, whichQas specifically pointed out below, may be the result of the total treatment of a saturated hydrocarbon in accordance with the present invention- The equation obviously is not intended to show how the reactions take place in the final While it isto be understood that the present I invention is not to be construed as being limited by any theory expressed herein, I am setting plex, which may be considered a pseudoester, as

It further appears that when. this loose complex is treated with an alkali, as hereinafter described, it is converted into a carbinol of the type referred to in Equation I, as follows:

In I I-o-EI By increasing the concentration of acetone and sulfuric acid above that contemplated in- Equation I, it may be considered that an additive carbinol, after neutralization, is first produced as indicated generally in Equation I, and that dehydration occurs to yield an additive alkylene,

1 which is indicated in a general way by the following equation:

H OH H H:

plex of the following structure:

- I a in ac-o-s'-o-c-Hcm n on It further appears that in the presence of the alkali under the conditions of treatment described in detail below, reaction occurs in the following manner to produce an additive alkylene: a

(IIb) In this case, when mobile hydrogen is present, as-is the case where there is used in the process acetone or any other ketone having at least a mcthylcnegroup with one mobile hydrogen adjacent to the carbonyl group, the change indicated in Equation no can occur, the dehydration taking place with the mobile hydrogen of the methyl group.

The dehydration might, however, under regulated conditions as described below take place at the hydrocarbon group involving another hydrogen of the hydrocarbon. For example, if there is employed a higher concentration of acetone and sulfuric acid than contemplated in Equation II, or if heat and dry alkali are used in the subsequent treatment as hereinafter described, the additive alkylene produced as generally indicated by Equation II may be converted into an additive iso-alkylene, as indicated in a general way by the following equation: 7

(III) As indicated, the additive alkylene produced according to Equation ILis transformable into the additive iso-alkylene produced in accordance with Equation III. However, the reaction is not readily reversible. Therefore, it is analogous to the eugenol-isoeugenol transformation to a certain extent. I

With reference to the theoretical explanation of the change indicated generally in Equation III,

it appears that under the conditions of operation referred to, there is formed a complex of the following structure:

It further appears that upon treatment with alkali, as hereinafter described, an iso-alkylene is formed as follows:

The type of additive alkylenes produced in accordance with Equations II and III can be readily changed into carbinols, the isopropyl or isopropylidene group being either changed back to acetone or to isopropyl alcohol, or can be easily oxidized, even to a mixture of acids. The remaining hydrocarbon radicle can either condense to higher hydrocarbons or undergo other changes to form alkylenes proper or alcohols.

If, by theadjustment of the concentration of acetone and sulfuric acid the general process is carried farther than indicated by the preceding equations, alkylene proper may be produced according to the following equation (in which one more carbon atom from the saturated hydrocarbon-radicle R is free to show the changes) In connection with the theoretical explanation of the production of an alkylene proper in accordance with Equation IV, it is pointed out that under the conditions of operation referred to, there apparently is formed a complex of the following structure:

It further appears that in the subsequent treatment'with alkali as hereinafter described in detail, the following reaction takes place:

It will be apparent from Equation IVb that in this case there has been complete dehydration. This is due to the excess of alkali present and the action of heat, which may merely be thetheat of reaction. It will be further noted that there is also produced an unsaturated compound from acetone, but where even a slight amount of water is present this compound is converted into isopropyl alcohol as follows:

ing of the hydrogen atoms in the end hydrocarbon group is a well known phenomenon in organic chemistry due to the action of alkali or heat, or

both.

The product resulting from Equation IV can be converted into an alcohol in accordance with the following equation:

With reference to the theoretical explanation of such conversion of a saturated hydrocarbon into an alcohol, it appears that under the conditions of operation hereinafter referred to there is formed a complex of the following structure:

It further appears that in the subsequent treatment in the presence of alkali and water under the conditions of operation hereinafter described in detail, the following reaction occurs:

The end product indicated in the equation may be isopropyl alcohol, for example.

If desired, the alcohol produced in accordance with Equation V may be converted into an aldehyde in accordance with the following equation:

Referring to the theoretical explanation of the production of aldehydes as indicated in Equation VI, it is to be noted, as hereinafter pointed out in detail, that in the production of aldehydes a. very high concentration, usually about nine molecular equivalents, of sulfuric acid must be used.

A possible theoretical explanation in graphic form of the formation of an aldehyde in the subsequent treatment of the suggested complex with alkali, as described below, would be as follows:

As pointed out below under Example 6, substantial excess of alkali should be avoided in the reaction indicated immediately above.

It will be apparent from the above that my process is based (a) upon the formation of carbinols, (in accordance with Equation I), and alkylenes (in accordance with Equations II, III and IV) and (b) upon the direct decomposition and transformation of these alkylenes to form alcohols (according to Equation V) and aldehydes (according to Equation VI). Polymerization and condensation products may also be formed from the alkylenes, as will be apparent.

For the purpose of specific illustration of the several reactions which may be caused to take place when an aliphatic or cyclic saturated hydrocarbon is reacted with an aliphatic aldehyde or ketone in the presence of sulfuric acid, several examples or different embodiments of the process are set forth below.

Example 1 I have found that practically any amount of any aliphatic aldehyde or any aliphatic ketone, especially acetone, together with sulfuric acid,

reacts with aliphatic or cyclic saturated hydrocarbons to give certain amounts, mostly mixtures, of unsaturated compounds and alcohols, aldehydes or polymerization and condensation products. For the present example I have selected a mixture of hydrocarbons nearly gaseous at ordinary temperature as they are found in petroleum ether, mostly pentanes and hexanes. Still lower hydrocarbons can be dissolved in, the aldehyde or ketone to be used but'in the present case it is unnecessary. In this example the saturated hydrocarbons in petroleum ether are reacted with acetone in the presence of sulfuric acid.

I.first take one molecular equivalent of petroleum ether. This" equivalent refers back to the pure hydrocarbons and is used in this sense throughout the present description, the fact being emphasized that in each case in order .to obtain best results the equivalents must be calculated according to the amounts and purity of the hydrocarbons present. In the present case where petroleum ether is employed, the equivalent means approximately forty parts by volume. The petroleum ether is then mixed with about onehalf of one molecular equivalent of sulfuric acid,

which inthe present case is approximately fifteen parts by volume of concentrated sulfuric acid (66 B.). Thecether and acid are mixed in a suitable apparatus of the character hereinafter described,'which apparatus is suitable for use for all of the reactions hereinafter set forth.

-When the hydrocarbons and sulfuric acid are mixed thetemperature in all cases should be lowered to approximately 5 C.

The apparatus in which the ether and acid are mixed is preferably an acid-proof vessel provided with a mechanical stirrer which is preferably .run by motor. The apparatus must either 'be provided with a water jacket or must be immersed in running water. In the upper part of the apparatus an opening should be provided for the introduction of the materials employed.

, Throughout the time of adding and stirring the sulfuric acid with the petroleum ether, the. mass should be continuously cooled to about 5 C. as stated above. When the mixing is completed I then add to the cooled mixture very gradually while maintaining the mass at a temperature not substantially in excess of 10 0., not less than one and not more than two molecular equivalents of pure dry acetone. In this example the acetone would be used to the extent of thirty to sixty parts by volume. ,The addition of the acetone should be gradual and would generally require approximately "fifteen minutes, after which the mixing is continued ,forthirty minutes more. Hence, the'total time of treatment from the beginning of the addition of the acetone should be,

about forty-five minutes. Of course, if more than fifteen minutes were consumedin adding the acetone, the total reaction time should be prolonged proportionately.

Thereafter; whilecontinuing the stirring and cooling, there is added sodium carbonate made into a paste with cool water, until the mixture is completelyneutralized. The mixture is then diluted with water in an amount sufficient to dissolve all sulfate and remaining carbonate. preferred practice the diluting water is'made, slightly alkaline with caustic soda. Upon dilution' a reddish fragment oil-rises to the top of the mass and is separated. The product is washed several times with water? and preferably fractionated, preferably with reduced pressure.

The apparatus employed in the above described process is preferably provided with a condenser, which may be an ordinary cold water condenser, so that all of ithe gases and superfluous acetone which might escape during the neutralization butyl carbinols. There are also formed in the reaction unsaturated additive compounds of the type hereinafter described and compounds formed by the condensation of acetone with the side chains, but the majority of the reaction products are carbinols of the type indicated above in Equation I.

The same reaction with practically the same results in principle is applicable to all other saturated aliphatic and saturated cyclic hydrocarbons and to their mixture in crude petroleum or any fraction or fractions of crude petroleum.

Example 2 Under the same conditions and in the same apparatus as' described under Example 1, I mix one molecular equivalent of comparatively pure hexane, with not less than one and not more than two molecular equivalents of concentrated sulfuric acid. To this mixture is added not less than one and not more than two molecular equivalents of pure dry acetone. The temperature of the reaction mass should be kept at about 15 C. and 'the total time for the reaction is about one hour.

' At the end of this time the mass is neutralized and diluted in the manner described-above and CH3) group. All hydrocarbons of the foregoing type including mixtures thereof in crude petroleum or any fraction or fractions of crude petroleum can be treated in the foregoing manner and give the same or substantially the same results.

Example 3 When the neutralized mixture described in the preceding example is not diluted with water, but

suflicient-sodium carbonate is added to make it nearly solid, and the resulting mass then mixed with about 10 per cent. of its bulk of powdered dry sodium hydroxide and slowly warmed over asbestos at a temperature of about 50 to 60 C. for about two hours, acetone is evaporated and the additive alkylene produced in accordance with Equation II is changed into its iso-compound. In the present case where hexane. was used the compound produced (in accordance with Equation III) is 1,1 dimethyl, 2 pentylethylene. While there are a number of other ways to perform this transformation of the substituted or additive alkylenes into their iso-compounds, I prefer to employ the method described.

Example 4 When the original mixture of hexane, concentrated sulfuric acid and acetone described in Example 2 is mixed for about three hours instead of only one hour, as set forth under Example 2, and is then neutralized and diluted, it is found that isopropyl alcohol is formed, or original acetone as the case may be, in the dilute solution and there is also produced an oil which is essentially an alkylene of the type produced in accordance with Equation IV. Where, as in the present case, hexane is originally treated, the alkylene will, of course, be hexylene. There are a number of ways to form this type of alkylenes, namely, to keep an additive alkylene or additive isoalkylene produced in accordance with Equations II and III in a dilute acid solution of proper strength, say 10 per cent. sulfuric acid, but the method specifically described above is preferred. 1

The foregoing reactions described in the pr ceding example are also applicable to any s turated hydrocarbon. Cyclic paraflins give re ctions in accordance with Equations 1, II and III, but in some cases their cycle can be disrupted, and they also form respective alkylenes of straight chain type as produced in accordance with Equation IV. However, as I have found, other changes might take place and an additive isoalkylene of the type produced in accordance with the Equation III may be preserved.

Crude petroleum is also changed in the above referred to manner into fragrant oils when products of the type produced in accordance with Equations I, II and IV are present although when a product of the type produced in accordance with Equation III is present -it sometimes has quite a disagreeable odor, especially when it is derived from one of the cyclic paraffins. The oils referred to have properties closely approximating the properties of vegetable drying oils and in some cases even surpass them. 4 a

As will be apparent, alkylenes proper of the type produced in accordance with Equation IV may be used for the production of alcohols, but in their crude mixture there are generally other substances present which give rise to resinification with concentrated sulfuric acid and, therefore, the following method for the production of alcohols is preferred.

Example 5 the mass is maintained at about 15 C. and the time of the reaction is about one hour. The resulting mixture is then neutralized with sodium carbonate in paste form, although here as well as in the processes described other carbonates or hydroxides, such for example, as calcium hydroxide Ol calcium carbonate can also be used. The neutralized mass is then diluted with water.

. As a result of this process decyl alcohol is produced.

The'same process may be used for mixtures of hydrocarbons or for crude petroleum and its fractions. For example, I may mix forty-five parts by volume of ordinary commercial gasoline, ninety parts by volume of concentrated sulfuric acid, and ninety parts by volume of pure dry acetone. Sodium carbonate in an amount sufficient to neutralize the acid present is mixed with about fifty parts by volume of cold water and the mixture is neutralized with this paste. About two hundred parts by volume of water are then added. Thereafter steam is circulated through the jacket surrounding the reaction vessel and acetone, isopropyl alcohol and the more volatile alcohols from the gasoline hydrocarbons distill over. The remaining alcohols consisting mostly of amyl, hexyl, heptyl and octyl alcohols are then separated from the mass and are fractionated or otherwise treated. Primary and secondary alcohols are separated in the well known chemical way. The reaction, in general way, is as follows:

For primary alcohols:

H a ac z=n+noa nc-c ion t t For secondary alcohols:

R H R R:C=(|3H+HOH EMF-(I111 For tertiary alcohols:

Tertiary alcohols may, of course, also be formed in accordance with the Equation I under Example 1. Quaternary hydrocarbons may sometimes cause the resinification of the mixture, but they are preferably attacked in one of their primary (CH3) side chain groups to form also primary alcohols.

In analogous way this is also true in general about the formation of alkylenes proper as in Example 4. The original quaternary hydrocarbons or in some cases even the original tertiary hydrocarbons may sometimes form either internal double bonds or be attacked in a primary group (-CH3) in a side chain; The resulting alcohols formed as in Example 5 are .then structurally analogous to the alkylenes proper;

As will be apparent the present process is suitable for the treatment not only of hydrocarbons which are liquid at normal temperatures but also hydrocarbons which are either gaseous or solid at normal temperature. When gaseous hydrocarbons are employed they are dissolved in acetone or the like and the process is carried out under pressure. When solid hydrocarbons are treated it is also preferable to dissolve these in the acetone or the like.

In the above example there has been described the treatment of comparatively pure decane and also ordinary commercial gasoline. As will be apparent, the process described is also suitable for the treatment of crude petroleum. Where crude petroleum is treated under approximately the same conditions as described above in connection with the treatment of gasolirue/there is produced a very fragrant spicy oil from which solid alcohols separate very readily on cooling. The oil mixture may be used as such or the alcohols may be separated by steam distillation or fractionation.

The formation of alcohols from cyclic saturated hydrocarbons is analogous to the above described format on of alcohols from the straight chain satura d hydrocarbons. For example, when cy-.'

clohexane, which is a typical cyclic paraflin, is

reacted with acetone in the presence of sulfuric acid as an activating agent, and the resulting mass neutralized as described above, the forma-' tion of alcohol takes place in the following man- As is apparent, the three equations set forth immediately above are intended merely to india cate-in a general way the production of an alcohol from cyclohex'ane by the treatment of the same'with acetone and sulfuric acid and the subsequent treatment with alkali as described above.

The first of the three equations, for example,

merely indicates in a general way the end prodnot which results from cyclohexane and acetone during the treatment in the presence of sulfuric acid and the subsequent treatment with alkali; A Theoretically, the complete reaction by which the end product in the first of the' three equations referred to is formed involves the formation of a complex of the following composition:

and the reaction of this complex with alkali, such as sodium carbonate, as follows:

The product thus produced is then converted into an alcohol as indicated in a general way in thesecond and third of the three equations referred to.

Example 6 are required where aldehydes are to be produced from lower hydrocarbons, the production of alprocess is carried out in an apparatus similar to that-described above and under conditions of reduced temperature as set forth in connection with the preceding example. In a specific case, one

molecular equivalent of kerosene, not less than 4 six and not more than nine molecular equivalents of concentrated acid, and not less than four and not more than 'six molecular equivalents of acetone are mixed together, the mass being stirred and cooled as described above. By way of more specific illustration, sixty parts by volume of kerosene, two hundred and seventy parts by volume of concentrated sulfuric acid and one hundred and fiftyparts by volume of acetoneare mixed, stirred and cooled. r

The reaction is permitted to proceed for about forty-five minutes. Thereafter the acid mass is neutralized, as with sodium carbonate, the alkali employed for neutralization being used only in suiiicient amount to react with the acid present.

Excessive alkali during the neutralization must be avoided. After neutralization the mass is diluted with water and aldehydes, in some cases mixed with'ketone's, rise to the top of the mass in the form 'of an oil of very pleasant. odor which is generally pinkish in color. If desired, the whole mixture, that is, the oil and aqueous solution may be'iiltered toremove solid aldehydes and ketones and also a small proportion of carbinols from the tertiary hydrocarbons and condensation products, mostly from the quaternary hydrocarbons, although I have found that, these latter hydrocarbons are generally attacked in their primary side chains to form aldehydes; Cyclic parafllns usually remain in the form of additive doublebonded compounds although the cycle may be readily broken and the respective ,aldehydes' formed. The above reaction proceeds substantially as follows:

| l/ v a-c=o on, no mom),

(Double bond severed) H on OK l OH OH, (In alkaline solution) It is evident, as shown in the equations, that a what takes place is an-aldehydo ketonic disruption of the double bond in the additive-isoalkylene set forth as the starting point in the above equations,and which is formed asvan intermediateproduct in accordance with Equations 1, H, and III set forth above. Where an aliphatic aldehyde is used'in the practice of the process, naturally two aldehydes are formed. Sometimes evenacetone may form small quantities of acetic aldehyde in the casedescribed The above referred to treatment is applicable to all saturated hydrocarbons and cycloparafilns not only in pure condition but also in mixtures as in crude petroleum or its fractions; with pure hydrocarbons, pure aldehydes are formed. In the event that it is desired to treat'gaseous hydrocarbons,-it is preferable to dissolve the gases in and at a temperature of approximately 0 C-. and not above 5 C.

Example 7 When sulfuric acid is employed greatly in excess of theamount of the aliphatic aldehyde or ketone employed to react with a saturated hydrocarbon, the reaction which takes place causes the production primarily of higher hydrocarbons formed by the condensation of the hydrocarbons used. For example, one part by volume of a saturated aliphatic or cyclic hydrocarbon either as such or in mixtures may be mixed with one part of acetone and three parts of sulfuric acid. The products formed are mostly'higher hydrocarbons. When the amounts of ketone and sulfuric acid are reversed and the ketone is present in substantial excess over the sulfuric acid, doublebonded hydrocarbons are first formed by the reaction of the saturated hydrocarbon with the ketone present and these double-bonded hydrocarbons can absorb another molecule of the ketone-at their double bonds and thus additional condensation products may be formed. In the same way, where aliphatic aldehydes are used, higher polymerization products can be formed from saturated aliphatic hydrocarbons and cycloparafiins.

The foregoing is set forth to show that I am perfectly aware of the fact that by other combinations than those specifically described different products may be produced. While I have conducted numerous experiments using all aliphatic aldehydcs and ketones which are accessible and have found that practically the same results are obtained therewith, I have specified above for the sake of illustration the aldehydes and ketones by the use of which the desired products can be made most simply and inexpensively and, for that reason. be of greater usefulness in general than those made by the use of less readily accessible or more expensive aldehydes and ketones.

As described in detail above, all of the desired products produced in accordance with the present invention by the reaction of aliphatic aldehydes and ketones with saturated aliphatic hydrocarbons and cycloparaiiins in the presence of an activating agent of the character described above are formed as the result of the action of the carbonyl group common to aliphatic aldehydes and ketones upon the saturated hydrocarbon under treatment. Also the formation and production of the products principally desired, such as alcohols and aldehydes depend upon the previous formation of compounds similar to those produced in accordance with Equations I, II, III and IV set forth above, no matter what aliphatic aldehyde or ketone is used and regardless of the proportions employed. Even if polymerization or condensation products are formed the complete reaction involves the several intermediate reactions illustrated by Equatioiis I, II, III and IV appearing above.

As indicated above, there are numerous possible modifications of the general reaction between a saturated hydrocarbon and an aliphatic aldehyde or ketone and anactivating agent such as sulfuric acid, with the production of numerous different products. However, as pointed out above, the several reactions which may be caused to take place depend upon the action on the saturated hydrocarbon under treatment of the carbonyl group common to aliphatic aldehydes and ketones. As has been described above, by varying the regulation .or control of the general reaction, the various stages through which the reaction may proceed can be controlled. For example, if

it is desired to produce from a saturated aliphatic or cyclic hydrocarbon an additive carbinol by the use of acetone and sulfuric acid, there should in general, be employed one molecular equivalent of the hydrocarbon and up to one-half molecular equivalent of the sulfuric acid. While, in general, there should be employed one molecular equivalent of acetone, the exact amount of acetone employed may be varied. For example, I may use from one to two molecular equivalents of acetone where the quantitative production of carbinols is desired.

Further, when it is desired to produce from an aliphatic orcyclic saturated hydrocarbon, additive alkylenes by the use of acetone and sulfuric acidwthe materials are employed in the proportions of one molecular equivalent of hydrocarbon, from one to two molecular equivalents of acetone and from one to two molecular equivalents of sulfuric acid. The proportions are the same where it is desired to produce additive isoalkylenes, the treatment of the materials in the proportions specified being followed by the heating of the mass withdry alkali.

Further, where it is desired to produce alkylenes proper from saturated aliphatic hydrocarbons by the use of acetone and sulfuric acid, the ingredients are mixed in the proportions of one molecular equivalent of hydrocarbon, from one to two molecular equivalents of acetone and from one to two molecular equivalents of sulfuric acid. As will be noted these proportions are the same as indicated above for the production of additive alkylenes and additive isoalkylenes. However, as set forth, in the case of the production of additive isoalkylenes the treatment involves heating the reaction mass with dry alkali. Where it is desired to produce alkylenes proper instead of additive alkylenes, the reagents are employed in the same proportions but the reaction is continued from one to three hours.

Further, where it is desired to produce alcohols from alkylenes proper, this can be accomplished, as pointed out above, by the use of larger amounts of sulfuric acid in order to form sulfuric acid esters of the respective alcohols and subsequently adding water to cause the esters to break down and liberate the alcohols themselves. In general, when it is desired to produce alcohols in this manner from aliphatic or cyclic saturated hydrocarbons by the use of acetone and sulfuric acid, the materials are mixed in the proportions of one molecular equivalent of hydrocarbon, three to four molecular equivalents of acetone, and three to four molecular equivalents of sulfuric acid.

Further, when it is desired to form aldehydes through, the stage of additive isoalkylenesof the type produced in accordance with Equation III set forth above, this is accomplished by the addition of greater amounts of sulfuric acid and neutralizing and dissolving the mass in mild alkaline solution, such as sodium carbonate solution. For example, when aldehydes are produced from saturated aliphatic hydrocarbons by the use of acetone and sulfuric acid, the materials are employed in the proportions of one molecular equivalent of hydrocarbon, from four to six molecular equivalents of acetone and from six to nine molecular equivalents of sulfuric acid. As pointed out in detail above ln Example 6, this treatment is followed by neutralization and solution in mild alkaline solution.

As will be apparent from the foregoing, all of the products described are obtainable through r 2,011,199 the reaction of an aliphatic or cyclic hydrocarbon,

an' aliphatic aldehyde or ketone and a chemical activating agent such as sulfuric acid, the ingredients being. employed in the proportions of one molecular equivalent of hydrocarbon, from four to six molecular equivalents of the reagent containing a carbonyl group, say acetone, and from six to ninemolecular equivalents of sulfuric acid. Where in the subjoined claims the term "water derivative of an oxide is employed, it is to be understood that the term refers to a compound which may be derived from an oxide by the action of water on it.

The term activating agent" as employed in thespeciflcation and claims is intended to cover an agent which activates or promotes reaction between a saturated aliphatic orcyclic hydrocarbon and an aliphatic aldehyde or ketone whereby polymerization or condensation products are obtained; As pointed out above, where the saturated hydrocarbon is treated according to the present invention with analdehyde in the presence of an activating agent, polymerization prod- .ucts are obtained, whereas condensation products are obtained by the practice of the present invention when the saturated hydrocarbon is treated with a ketone in the presence of an activating agent. Several different activating agents have been set forth above including those of both scientific and commercial interest. As

has been described, sulfur oxides and especially that the details of procedure, the arrangement of-steps and the proportions of ingredients may I be variously modified without departing from the spirit of the invention or.the scope of the subjoined claims. j

I claim: 1. In a process ofthe character described, the step which comprises reacting a hydrocarbon compound selected from the group consisting of saturated aIiphatic and saturated cyclic'hydrocarbons with at least one molecular equivalent of a reagent containing a carbonyl group selected from the, group consisting of aliphatic aldehydes and ketones in the presence of an activating agent, said. reagent containing a carbonyl group being predominantly free from water.

2. In a process of the character described, the

step which comprises reacting a hydrocarbon no compound selectedfrom the group consisting of saturated aliphatic and saturated cyclic hydro O carbons with at least one molecular equivalent" f a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes i5 and ketones in the presence of an'activating agent consisting substantially of a sulfur compound selected from the group consisting of acidforming sulfur oxides-and sulfuric acid, said reagent containing a carbonyl group being predominantly free from water. a 3. In a process of ,the character described, the step which comprises reacting a hydrocarbon compound selected from the group consisting of saturated aliphatic and saturated cyclic hydrocarbons with at least one molecular equivalent As has beenpointed of a reagentcontaining a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of an activating agent consisting substantially of an acid-forming sulfur oxide, said reagent containing a carbonyl group being predominantly free from water.

4. In a process of the character described, the

'step which comprises reacting a hydrocarbon"- saturated aliphatic and saturated cyclic hydro-- carbons with at least one molecular equivalent of a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of an activating agent consisting substantially of an alkali-forming metal compound selected from the group consisting of oxides and hydroxides of alkali- 'forming metals, said reagent containing a carbonyl group being predominantly free from water.

In a process of the character described, the step which comprises reacting a hydrocarbon compound selected from the group consisting of saturated aliphatic and saturated cyclic hydrocarbons with at least one molecular equivalent of a reagent containing a carbonyl group s'elected from the group consisting of aliphatic aldehydes and ketones in the presence of an activatlng agent consisting substantially of an alkaliforming metal oxidepsaid reagent containing a carbonyl group being predominantly free from water.

7. In a process of the character described, the

step which comprises reacting a hydrocarbon compound selected fromthe group consisting of saturated aliphatic and saturated cyclic hydrocarbons with at least one molecular equivalent of a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of an activating agent consisting substantially of an alkali-forming metal hydroxide, said reagent containing a carbonyl group being predominantly free from water.

8. In a process of the character described the step which comprises reacting a hydrocarbon compound'selected from the group consisting of saturated aliphatic hydrocarbons and saturated cyclic hydrocarbons with at least one molecular equivalent of an aliphatic ketone in the presence of an activating agent.

, 9. Ina process of the character described the step which comprises reacting a'hydrocarbon compound selected from the group consisting of saturated aliphatic hydrocarbons and saturated cyclic hydrocarbons withat least one molecular equivalent of an aliphatic ketone in the presence of an activating agent consisting substantially of a sulfur compound selected from the group consisting of acid-forming sulfur oxides and sulfuric acid.

10. In a process of the character described the step which comprises reacting a hydrocarbon compound selectedfrom the group consisting of saturated aliphatic hydrocarbons and saturated hydrocarbons, saturated cyclic hydrocarbon?Y and cyclic .hydrocarbonswith' at least onemolecular equivalent of an aliphatic ketone inthe presence of an'activating agent comprising sulfuric acid. 12. 'In'a'process of treating saturated aliphatic hydrocarbons, saturated cyclic hydrocarbons, and mixtures containing the same, the step which comprises reacting upon the saturated hydrocarbons under treatment with at least one molecular equivalent of acetone in the presence of sulfuric acid. 13. In a process of treating saturated aliphatic mixtures containing the same, the step hich comprises subjecting the material under t eatment to the action of acetone and sulfuric acid, such agents being present in the proportion of one molecular equivalent of saturated hydrocarbons, from one to five molecular equivalents of acetone, and from one-half to nine molecular equivalents of sulfuric acid.

14. In a process of treating material containing saturated hydrocarbons selected from the group consisting of saturated aliphatic hydrocarbons and saturated cyclic hydrocarbons, the step which comprises intimately contacting the material under treatment with a reagent containing a carbonyl group selected from the group consist,

ing of aliphatic aldehydes and ketones and a chemical activating agent at a temperature of approximately from C. to 15 0., such agents being present in the proportions of one molecular equivalent of saturated hydrocarbons, up to two molecular equivalents of said reagent containing a carbonyl group, and up to two molecular equivalents of the activating agent.

15. In a process of treating material containing saturated hydrocarbons selected from the group consisting of saturated aliphatic hydrocarbons and saturated cyclic hydrocarbons, the step which comprises intimately contacting the material under treatment with acetone and sulfuric acid at a temperature of approximately from 41 C. to 15 C., such agents being present in the proportions of one molecular equivalent of saturated hydrocarbons, up to two molecular equivalents of acetone, and up to two molecular equivalents of sulfuric acid.

16. In a process of the character described, the step which comprises reacting a saturated hydrocarbon compound selected from the group consisting of saturatedaliphatic and cyclic hydrocarbons with a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of sulfuric acid, such reagents being present in the proportions of one molecular equivalent of saturated hydrocarbon, from one to two molecular equivalents of said reagent containing a carbonyl group, and from one to two molecular equivalents of sulfuric acid.

17. In a process of treating saturated aliphatic hydrocarbons, saturated cyclic hydrocarbons, and mixtures containing the same, the step which comprises subjecting one molecular equivalent of the material to be treated to the action of from one to two molecular equivalents of acetone and from one to two molecular equivalents of sulfuric acid.

18. A process of the character described which comprises reacting a hydrocarbon compound selected from the group consisting of saturated aliphatic and cyclic hydrocarbons with a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of sulfuric acid, such reagents being present in the proportions of one molecular equivalent of hydrocarbon, from one to two molecular equivalents of said reagent containing a carbonyl group, and from one to two molecular equivalents of sulfuric acid, and treating the resulting mass with alkali.

19. The process of treating saturated aliphatic hydrocarbons, saturated cyclic hydrocarbons, and mixtures containing the same which comprises subjecting the hydrocarbon material under treatment to the action of acetone and sulfuric acid, such reagents being present in the proportions of one molecular equivalent of hydrocarbon, from one to two molecular equivalents of acetone, and from one to two molecular equivalents of sulfuric acid, and treating the resulting mass with dry caustic alkali.

20. In a process of the character described, the step which comprises intimately contacting for a period of from one to three hours a hydrocarbon compound selected from the group consisting of saturated aliphatic and cyclic hydrocarbons, a reagent containing a carbonylgroup selected from the group consisting of aliphatic aldehydes and ketones, and sulfuric acid, such reagents being present in the proportions of one molecular equivalent of hydrocarbon, from one to two molecular equivalents of said reagent containing a carbonyl group, and from one to two molecular equivalents of sulfuric acid.

21. In a process of the character described, the step which comprises intimately contacting for a period of from one to three hours a saturated aliphatic hydrocarbon, acetone and sulfuric acid, such reagents being present in the proportions of one molecular equivalent of hydrocarbon, from one to two molecular equivalents of acetone, and from one to two molecular equivalents of sulfuric acid.

22. In a process of the character described, the step which comprises reacting a hydrocarbon compound selected from the group consisting of saturated aliphatic and cyclic hydrocarbons with a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of sulfuric acid, such reagents being present in the proportions of one molecular equivalent of hydocarbon, from three to four molecular'equivalents of said reagent containing a carbonyl group, and from three to four molecular equivalents of sulfuric acid.

23. In a process of treating saturated aliphatic hydrocarbons, saturated cyclic hydrocarbons, and mixtures containing the same, the step which comprises subjecting the hydrocarbon material under treatment to the action of acetone and sulfuric acid, such agents being presentin the proportions of one molecular equivalent of hydrocarbon, from three to four molecular equivalents of acetone and from three to four molecular equivalents of sulfuric acid.

24. A process of the character described which comprises reacting a hydrocarbon compound selected from the group consisting-of saturated aliphatic and saturated cyclic hydrocarbons with at least one molecular equivalent of a reagent con taining a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of an activating agent selected from the group consisting of acid-forming sulfur oxides and sulfuric acid, said reagent containing a carbonyl group being predominantly free from water, and thereafter treating the resulting mass with alkali. V,

25. The process of treating saturated aliphatic hydrocarbons, saturated cyclic hydrocarbons and mixtures containing the same which comprises subjecting the hydrocarbon material under treatment to the action of at least one molecular equivalent of a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of sulfuric acid, said. reagent containing a carbonyl group being predominantly free from water, and thereafter treating the mass with alkali.

26. Ina process of the character described, the step which comprises reacting a hydrocarbon compound selected from the group consisting of saturated aliphatic and cyclic hydrocarbons with a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of sulfuric acid, such agents being present in the proportions of one molecular equivalent of hydrocarbon, from four to six molecular equivalents of said reagent containing a carbonyl group, and from six to nine molecular equivalents of sulfuric acid.

27. The process which comprises reacting a hydrocarbon compound selected from the group consisting of saturated aliphatic and cyclic hydronarbons with a reagent containing a carbonyl group selected from the group consisting of aliphatic aldehydes and ketones in the presence of sulfuric acid, such agents being present in the proportions of one molecular equivalent of hydrocarbon, from four to six molecular equivalents of said reagent containing a carbonyl group, and from six to nine molecular equivalents of sulfuric acid, thereafter neutralizing the mass with alkali, and diluting the resulting mass with water.

28. The process which comprises intimately contacting one molecular equivalent of a saturated aliphatic hydrocarbon, from four to six molecular equivalents-of acetone, and from six to nine molecular equivalents of sulfuric acid, thereafter neutralizing the mass with alkali, and diluting the resulting mass with water.

JOSEPH J. PELC. 

